JPWO2013187324A1 - Board sheet and touch panel - Google Patents

Abstract

A transparent electrode 13 made of a conductive polymer and a metal wiring 14 connecting the transparent electrode 13 and the connector connecting portion 18 are provided on the translucent substrate 12, and the transparent electrode 13 and the metal wiring 14 are covered. Providing the substrate sheet 11 provided with the protection against the transparent electrode 13 and the corrosion of the metal wiring 14 with respect to the substrate sheet 11 provided with the protective layer 15. The protective layer 15 is a laminate in which a sulfur-resistant resist layer 17 that prevents sulfidation of the metal wiring 14 and a light-resistant resist layer 16 that absorbs ultraviolet rays are laminated on the base material 12. It was formed with a polyurea resin layer. [Selection] Figure 2

Description

  The present invention relates to a substrate sheet that can be used as an electrostatic sensor such as a touch panel, and a touch panel using the substrate sheet.

  A transparent conductive polymer is used for an electrode of an electrostatic sensor such as a touch panel. Since this transparent conductive polymer is significantly deteriorated by light, a protective layer is formed by a resist film containing an ultraviolet absorber to cover this electrode. Such a technique is described in, for example, Japanese Patent Application Laid-Open No. 2011-192150 (Patent Document 1).

JP 2011-192150 A

On the other hand, the metal wiring part for connecting the electrode and the external device has a problem that although there is no light resistance problem seen in the conductive polymer, the conductivity may be impaired by the reaction with the sulfur component. .
Then, an object of this invention is to provide the touchscreen formed using the board | substrate sheet | seat which not only protected with respect to the conductive polymer but was also protected from the corrosion of the metal wiring part.

In order to achieve the above object, the following substrate sheet is provided.
A substrate having a transparent electrode made of a conductive polymer and a metal wiring connecting the transparent electrode and the connector connecting portion on a translucent base material, and a protective layer covering the transparent electrode and the metal wiring is provided. It is a sheet, and a protective layer is a laminate in which a sulfur-resistant resist layer that prevents sulfidation of metal wiring and a light-resistant resist layer that absorbs ultraviolet rays are laminated in this order from the translucent substrate side. The resist sheet is a substrate sheet that is a polyurethane-polyurea resin layer.

For a substrate sheet having a transparent electrode made of a conductive polymer and a metal wiring, a sulfur-resistant resist layer that prevents sulfidation of the metal wiring and a light-resistant resist layer that absorbs ultraviolet rays are arranged in this order from the translucent substrate side. Since the protective layer made of the laminated body is provided, it is possible to prevent the transparent electrode from being deteriorated by ultraviolet rays and the metal wiring from being sulfided.
Since the sulfur-resistant resist layer is a polyurethane / polyurea resin layer, the gas barrier property can be improved by containing the polyurea component, and the sulfidation of the metal wiring can be effectively prevented.

The polyurethane / polyurea resin forming the polyurethane / polyurea resin layer has a polyisocyanate component in an amount 1.2 to 5.5 times the amount of the polyisocyanate component having an NCO group equivalent to the OH group of the polyol component. It can be set as the board | substrate sheet | seat which is resin which contained and hardened and formed the urea bond in addition to the urethane bond.
Polyurethane / polyurea resin forming the polyurethane / polyurea resin layer is 1.2 times to 5.5 times the amount of polyisocyanate component having an equivalent NCO group reacting with the OH group of the polyol component. Since the resin has a urethane bond and a urea bond that are contained and cured, the metal wiring can be protected from sulfurization.

A polyurethane / polyurea resin layer forming a polyurethane / polyurea resin layer can be a resin obtained by reaction-curing a raw material having an NCO group / OH group value of 1.2 to 5.5.
The polyurethane / polyurea resin forming the polyurethane / polyurea resin layer is a resin obtained by reaction curing of a raw material having an NCO group / OH group value of 1.2 to 5.5. A polyurethane / polyurea resin layer having a urea bond in addition to the bond is formed. Therefore, the crosslink density of the resin can be increased as compared with the case where no urea bond is formed. In other words, the distance between the molecular chains can be made close. Therefore, it is easy to prevent the sulfur component from entering, and the metal wiring can be protected from sulfidation degradation. Therefore, it can be set as the protective layer excellent in sulfidation resistance.

  The sulfur-resistant resist layer can be a resin layer having a higher crosslink density than the light-resistant resist layer. Since the sulfur-resistant resist layer has a higher crosslinking density than the light-resistant resist layer, the sulfur resistance can be improved.

  It can be set as the board | substrate sheet | seat whose light-resistant resist layer is a polyurethane-type resin layer. Since the light-resistant resist layer is a polyurethane-based resin layer, the adhesion with the sulfur-resistant resist layer can be improved.

  And a touch panel can be manufactured using said board | substrate sheet | seat. Since it is a touch panel provided with said board | substrate sheet | seat, it can be set as the touch panel which hardly raise | generates the modification | denaturation of an electrode and deterioration of metal wiring.

  According to the substrate sheet and the touch panel of the present invention, the transparent electrode made of a conductive polymer and the metal wiring can be protected from deterioration or sulfurization due to ultraviolet rays or sulfur components.

It is a top view of a substrate sheet. It is the SA-SA sectional view taken on the line of FIG.

The present invention will be described in more detail based on embodiments.
As shown in FIGS. 1 and 2, the substrate sheet 11 of the present embodiment includes a light-transmitting base material 12, a transparent electrode 13 made of a transparent conductive polymer formed on the base material 12, and It has a layer configuration including at least a metal wiring 14 for connecting the transparent electrode 13 to an external electric circuit, and a protective layer 15 covering the transparent electrode 13 and the metal wiring 14, and is a capacitance type. It can be used as a touch panel.

The substrate 12 is formed of a highly transparent resin film, for example, polyethylene terephthalate (PET) resin, polyethylene naphthalate (PEN) resin, polycarbonate (PC) resin, methacryl (PMMA) resin, polypropylene (PP) resin. , Polyurethane (PU) resin, polyamide (PA) resin, polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, triacetylcellulose (TAC) resin, cycloolefin polymer (COP), etc. be able to.
The substrate 12 may be subjected to a surface treatment by providing a primer layer that enhances adhesion to the conductive polymer, a surface protective layer, an overcoat layer for the purpose of preventing static charge, or the like.

  As the material of the conductive polymer that becomes the transparent electrode 13, a conductive polymer that can form a transparent layer is used. Examples of such transparent conductive polymers include polyparaphenylene or polyacetylene, PEDOT-PSS (poly-3,4-ethylenedioxythiophene-polystyrenesulfonic acid), and the like.

  Both the sulfur-resistant resist layer 17 and the light-resistant resist layer 16 have a high light transmittance in the visible light region, and these layers are transparent or almost transparent. Further, since the light-resistant resist layer 17 blocks ultraviolet rays, the light transmittance in the ultraviolet region (wavelength less than 400 nm) is almost zero.

The metal wiring 14 connects the connector connection portion 18 connected to an electric circuit such as an information processing device (not shown) provided outside the substrate sheet 11 and the transparent electrode 13.
The material of the metal wiring 14 is preferably formed from, for example, a conductive paste or a conductive ink containing a highly conductive metal such as copper, aluminum, silver, or an alloy containing these metals. Further, among these metals and alloys, silver wiring is preferable because it has high conductivity and is less likely to be oxidized than copper.

  The protective layer 15 is a layer that covers the transparent electrode 13 and the metal wiring 14, and is a layer formed by laminating a light-resistant resist layer 16 and a sulfide-resistant resist layer 17. The transparent electrode 13 and the metal wiring 14 are covered with a sulfur-resistant resist layer 17, and the light-resistant resist layer 16 is covered on the sulfur-resistant resist layer 17.

  The light-resistant resist layer 16 is a layer for protecting the substrate sheet 11 from scratches and the like, and protecting the transparent conductive polymer from ultraviolet rays, and is a layer containing an ultraviolet absorber in a transparent resin. As the transparent resin, a hard resin is selected. For example, an acrylic resin, a urethane resin, an epoxy resin, a polyolefin resin, or other resins can be used, but a raw material composition comprising a polyisocyanate component and a polyol component. It is preferable to use a polyurethane resin layer obtained by curing the product. This is because the hardness can be easily adjusted and the strength is high.

  When a polyurethane resin layer is used, aliphatic diisocyanate, alicyclic polyisocyanate, and arylaliphatic polyisocyanate are used as the polyisocyanate component in the raw material composition in consideration of weather resistance including yellowing. It is particularly preferred. More specifically, examples of the aliphatic diisocyanate include hexamethylene diisocyanate; examples of the alicyclic polyisocyanate include dicyclohexylmethane diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate; examples of the aryl aliphatic polyisocyanate include xylylene diisocyanate; Adduct type, burette type, isocyanurate type, and urethane imine type polyisocyanates can be used.

  Aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, para-phenylene diisocyanate; and their adduct types It is also possible to use isocyanates such as burette type, isocyanurate type and uretonimine type polyisocyanates.

The polyol component is obtained by adding low molecular weight polyols such as ethylene glycol, propylene glycol and glycerin; and polyphenols by adding alkylene oxide such as diethylene oxide, propylene oxide, 1,2-butadiene oxide and styrene oxide. Examples of the polyether polyol include polyester polyols obtained by a dehydration condensation reaction between the low molecular polyols and dicarboxylic acids such as adipic acid and phthalic acid.
Furthermore, acrylic polyol, polycarbonate polyol, polyurethane polyol, polycaprolactone polyol and the like can be mentioned.
The light resistant resist layer 16 contains an ultraviolet absorber. Various ultraviolet absorbers such as salicylic acid, benzophenone, benzotriazole, and hindered amine can be used as the ultraviolet absorber.

The average light transmittance of the light-resistant resist layer 16 in the visible light region of 400 nm to 800 nm is preferably 80% or more, and more preferably 85% or more.
The thickness of the light resistant resist layer 16 is usually 3 μm to 10 μm, preferably 6 μm to 8 μm. The reason is that if it is too thick, the flexibility is poor, and if it is too thin, the effect of light resistance is weakened.

The sulfidation resistant resist layer 17 is a layer mainly for preventing sulfidation of the metal wiring 14, and is formed of a polyurethane / polyurea resin layer. The polyurethane-polyurea resin forming the polyurethane-polyurea resin layer is a resin containing a polyisocyanate component in an amount larger than the amount of polyisocyanate component having an equivalent NCO group that reacts with the OH group of the polyol component. is there.
Since the raw material containing the polyisocyanate component in an equivalent amount or more with respect to the polyol component was used, an excess NCO group different from the NCO group forming the urethane bond reacts with moisture and further reacts with another NCO group to form a urea bond. Forming. Therefore, the polyurethane-polyurea resin is a resin having a urea bond in addition to a urethane bond, and is a resin having a higher crosslink density than a polyurethane resin having a urethane bond.

  Polyurethane / polyurea-based resin raw material containing a polyol component and a polyisocyanate component includes 1.2 to 5.5 times the amount of polyisocyanate having an equivalent NCO group that reacts with the OH group of the polyol component. It is preferable that the component is contained. If it is less than 1.2 times, the ratio of urea bonds decreases and the resistance to sulfidation becomes insufficient. On the other hand, if it is more than 5.5 times, the number of urea bonds increases, so that the sulfur-resistant resist layer 17 tends to be hard and brittle.

  Polyurethane / polyurea resins include (a) a copolymer in which a polyurethane polymer and a polyurea polymer are linked, (b) a mixture in which the polyurethane polymer and the polyurea polymer exist independently, and (a) The resin in any state of the mixture mixed with (b) is included.

When using a polyurethane-based resin for the light-resistant resist layer 16, the same components as the polyisocyanate component and the polyol component in the raw material composition for forming the light-resistant resist layer 16 can be used. By changing it, the sulfidation resistant resist layer 17 can be formed. Therefore, the adhesion between the light-resistant resist layer 16 and the sulfide-resistant resist layer 17 is high, and the protective effect of the transparent electrode 13 and the metal wiring 14 is enhanced.
In addition, since the sulfur-resistant resist layer 17 is directly laminated on the metal wiring 14, it is possible to reliably prevent the intrusion of sulfur components that would reach the metal wiring 14 through other layers.

The average light transmittance of the sulfide-resistant resist layer 17 in the visible light region of 400 nm to 800 nm is preferably 80% or more, and more preferably 85% or more.
The thickness of the sulfidation resistant resist layer 17 is usually 3 μm to 10 μm, preferably 6 μm to 8 μm. The reason is that if it is thicker than 10 μm, the flexibility is poor, and if it is thinner than 3 μm, the action of sulfidation resistance is weak, and if it is 6 μm to 8 μm, it is flexible and the sulfidation resistance is strong.

Thus, the protective layer 15 in which the light-resistant resist layer 16 and the sulfide-resistant resist layer 17 are laminated has the following advantages.
For example, considering that the protective layer 15 is formed in one layer having light resistance and sulfidation resistance to the same thickness as in the case of the two layers of the present invention, the content of the isocyanate component compared to the case of the two layers It is necessary to increase the amount of urea bonds. This is because if the same amount of isocyanate component as that in the case of two layers is contained, the crosslink density of the protective layer is lowered, and the sulfidation resistance is deteriorated. That is, in the case of one layer, the polyisocyanate component must be increased more than in the case of two layers, and there arises a disadvantage that the protective layer becomes hard. In addition, the cost of the raw material becomes high.

  Further, if the sulfur-resistant resist layer 17 is provided on the substrate 12 side and the light-resistant resist layer 16 is provided on the outside, the sulfur component entering from the side surface side of the substrate 12 can be effectively blocked. This is more preferable than the case where the light-resistant resist layer 16 is provided on the material 12 side and the sulfide-resistant resist layer 17 is provided outside.

Other layers other than the above layers can be provided as necessary. For example, a colored layer for imparting a color as a whole, a layer for changing the refractive index of light or polarizing the light, and the like can be mentioned.
In addition, in the structure of the board | substrate sheet | seat 11, the transparent electrode 13 and the metal wiring 14 should just be provided in a part of base material 12 surface, and may be provided in the whole surface. Moreover, you may provide in the front and back both surfaces of the base material 12 as needed.
The shapes of the transparent electrode 13 and the metal wiring 14 are not limited to the above shapes.

  In the manufacture of the substrate sheet 11, the transparent electrode 13 and the metal wiring 14 are printed and formed at predetermined locations on the transparent resin film to be the base 12. And the raw material composition used as the sulfur-resistant resist layer 17 and the light-resistant resist layer 16 is apply | coated on it, it is made to harden | cure, and the protective layer 15 is formed. Thus, the substrate sheet 11 can be obtained.

A substrate sheet (11) having the layer structure shown in FIGS. 1 and 2 was produced.
Example 1 :
On the substrate (12) made of a transparent PET resin film, a transparent conductive ink (manufactured by Olgacon P3000 AGFA) was screen-printed to obtain a rectangular transparent electrode (13). Moreover, it screen-printed with the silver ink (made by 7145 DuPont) on the base material (12), and the metal wiring (14) was obtained. Then, a sulfide-resistant resist layer (17) and a light-resistant resist layer (16) were sequentially provided on these by screen printing.
The lower sulfur-resistant resist layer (17) is formed from a raw material ink (NCO / OH = 2.2) in which an HDI-based isocyanate is mixed with a polyester polyol having a hydroxyl value of 36 mgKOH / g. 16) was formed from a raw material ink in which a polyester polyol was mixed with an HDI isocyanate (NCO / OH = 1.1) and a benzotriazole ultraviolet absorber was further added.

  Further, the tip of the metal wiring (14) was covered with carbon ink by printing to form a connector connecting portion (18) for connecting to an electric circuit. The connector connecting portion (18) has a portion not covered with a protective layer (15) (sulfur resistant resist layer (17) and light resistant resist layer (16)) on its surface. Thus, a substrate sheet (11) in which the transparent electrode (13) and the metal wiring (14) were covered with the protective layer (15) was obtained.

Examples 2 to 7 :
Substrate sheets (11) of Examples 2 to 7 were obtained in the same manner as in Example 1 except that the NCO / OH ratio of the sulfur-resistant resist layer (17) of Example 1 was changed to the values shown in Table 1 below.

Example 8 :
A substrate sheet (11) of Example 8 having a different order of lamination of the protective layer (15) from Example 1 was produced.
In Example 8, a light resistant resist layer (16) was formed in the lower layer, and a sulfide resistant resist layer (17) was formed in the upper layer.

<Light resistance test method, evaluation method>:
Using a sunshine weather meter, an accelerated light resistance test (Sunshine carbon arc light source in a 63 ° C. environment without water injection) in accordance with JIS K7350-4 was conducted.
The substrate sheets (11) obtained in Examples 1 to 8 were attached on a white mount and irradiated from the resist surface side for 300 hours, and the resistance value change rate (%) of the transparent electrode (13) was evaluated.

<Sulfuration resistance test method and evaluation method>:
Place sulfur powder near the substrate sheet (11) obtained in Examples 1 to 8 and leave it in a saturated sulfur vapor atmosphere at 85 ° C. covered with a petri dish for 300 hours and 500 hours. The resistance value change rate (%) of 14) was evaluated.
Note that “(disconnected)” in the table indicates that the measured value of the tester exceeded the displayable value of 2 MΩ.

<Method of crosslinking density evaluation (swelling test)>:
In the same manner as the formation of the light-resistant resist layer (16) of the substrate sheet (11) of Examples 1 to 8, only the light-resistant resist layer (16) is applied and formed into a sheet shape, which corresponds to Examples 1 to 8. A test piece consisting only of the light-resistant resist layer (16) was produced. These test pieces were immersed in toluene for 1 hour, and the weight change rate (%) was described in the locations corresponding to Examples 1 to 8 in Table 1, respectively.

In Examples 1 to 8, the light-resistant resist layer (16) in the protective layer (15) contains an ultraviolet absorber, and the transparent electrode (13) has a resistance value change, but the change is + 320% or less. In order to be usable as a touch panel, the conductivity is maintained.
Examples 1 to 5 have a sulfide-resistant resist layer (17) as a protective layer (15), and the metal wiring (14) maintains conductivity although the resistance value changes.
In Example 6, the metal wiring (14) was disconnected after 300 hours in the sulfidation resistance test, that is, the desired conductivity was lost. Moreover, it turned out that the weight change rate of a sulfur-resistant resist layer (17) is + 35%, and it is easy to permeate | transmit toluene.

In Example 7, the value of (NCO / OH) was large, the sulfide-resistant resist layer (17) was hard, and the obtained substrate sheet (11) was difficult to bend.
Example 8 has a configuration in which the protective layer (15) is laminated such that the light-resistant resist layer (16) is formed in the lower layer and the sulfide-resistant resist layer (17) is formed in the upper layer. In the sulfidation resistance test, the conductivity could be maintained after 300 hours and a certain sulfidation resistance was obtained, but after 500 hours, the metal wiring (14) was disconnected, that is, the desired conductivity was lost.

  The shapes, layer configurations, raw materials and the like described in the above embodiments and examples can be appropriately changed without departing from the gist of the present invention, for example, other known raw materials other than the above can be used. It is included in the scope of the technical idea.

DESCRIPTION OF SYMBOLS 11 Board sheet 12 Base material 13 Transparent electrode 14 Metal wiring 15 Protective layer 16 Light resistant resist layer 17 Sulfide resistant resist layer 18 Connector connection part

Claims (6)

A substrate having a transparent electrode made of a conductive polymer and a metal wiring connecting the transparent electrode and the connector connecting portion on a translucent base material, and a protective layer covering the transparent electrode and the metal wiring is provided. A sheet,
A substrate sheet in which a protective layer is a laminate in which a sulfur-resistant resist layer that prevents sulfuration of metal wiring and a light-resistant resist layer that absorbs ultraviolet rays are laminated, and the sulfur-resistant resist layer is a polyurethane-polyurea resin layer.   The substrate sheet according to claim 1, wherein the protective layer is a laminate in which a sulfide-resistant resist layer and a light-resistant resist layer are laminated in this order from the translucent substrate side.   3. The polyurethane / polyurea resin forming the polyurethane / polyurea resin layer is a resin obtained by reaction-curing a raw material having an NCO group / OH group value of 1.2 to 5.5. Board sheet   The substrate sheet according to any one of claims 1 to 3, wherein the sulfur-resistant resist layer is a layer having a higher crosslinking density than the light-resistant resist layer.   The substrate sheet according to any one of claims 1 to 4, wherein the light-resistant resist layer is a polyurethane resin layer.   A touch panel comprising: a display device; and the substrate sheet according to any one of claims 1 to 5 mounted on a screen of the display device.

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